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JOURNAL OF POLYMER SCIENCE: PART A-1

VOL. 8, 139-146 (1970)

Characterization of Styrene-Acrylonitrile Copolymer by Pyrolysis Gas Chromatography


R. W K O V I e and V. GNJATOVIC, Research Institute, I N A , Zagreb, Yugoslavia

Synopsis
Samples of styrene-acrylonitrile (SAN) copolymer of different compositions, molecular weights, block copolymers, and a blend of styrene and acrylonitrile homopolymen were prepared and characterized by the method of pyrolysis gas chromatography. On decomposition of SAN copolymer samples a t 645OC, eleven components were identified, the most important of them being styrene, acrylonitrile, and propionitrile. By examination of the pyrolyzate composition during pyrolysis of the SAN copolymer of different compositions, it was established that the propionitrile yield was definitely decreased when the acrylonitrile concentration in copolymer was about 60 mole-o/& Further, from the propionitrile yield, we could distinguish random SAN copolymer from the styrene-acrylonitrile homopolymer blend, and on the basis of propionitrile yield some information on the molecular structure of the copolymer could be obtained. The styrene yield depends linearly on the copolymer composition. This permits determination of copolymer composition on the basis of the styrene yield. Furthermore, the effects of decomposition temperature and of molecular weight on the yields of styrene and acrylonitrile were examined.

INTRODUCTION
There is a relatively small number of publications on the study of styreneacrylonitrile( SAN) copolymer by the method of pyrolysis gas chromatography.'+ According to Voight,' it was possible to identify SAN copolymer by this method. Lebe12 reported that this method could successfully be used to distinguish a homopolymer blend from the random SAN copolymer. Shibasaki and Kambe3-5 determined that on the basis of styrene and acrylonitrile yields it was possible to get data on the structural composition of the copolymer. These authors succeeded in identifying, in addition to styrene and acrylonitrile, benzene, a-methylstyrene, and ethylbenzene by this method. The latter two components were found in trace amounts only. We used the method of gas chromatography to separate acetonitrile and propionitrile from acrylonitrile and ethylbenzene, and a-methylstyrene from styrene; we identified eleven components which helped us to make a detailed study of the effect of the copolymer composition on the yields of the individual components of the pyrolysate. I n addition, the effect of the
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Q 1970 by John Wiley & Sons, Inc.

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decomposition temperature and the molecular weight on the yields of styrene and acrylonitrile monomers was examined.

EXPERIMENTAL
Monomers and Initiators
Acrylonitrile (AN), Carlo Erba, purity 99%, was treated with concentrated NaOH and then washed repeatedly with distilled water. After that it was dried and distilled over calcium hydride. Styrene (St) was polymer grade (produced by Organsko Kemijska Industrija, Zagreb), with no traces of polymers, purity 99.96% and containing 12 ppm of p-tert-butyl catechol. Lauroyl peroxide (Noury Van der Lande) and 2,2-azobis-2-methylpropionitrile (Eastman Organic Chemicals) were used without further purification.

Polymers and Polymer Blends


Samples of SAN copolymers of different composition were prepared by bulk polymerization a t 70 f 1Cin the presence of lauroyl peroxide. After a conversion of 3 4 % was reached, the polymer was precipitated with ethanol and then purified by precipitation with ethanol from an acetone solution. This procedure was repeated three times, after which the polymer was dried under vacuum to a constant weight. The composition of the prepared samples is shown in Table I.
TABLE I Composition of SAN Copolymer Samples
Sample no. AN in copolymer, mole-%.
12.5

28.8 38..5 47.5 58.0 62.0

77.0

* Calculated from nitrogen content (Kjeldahl).

Okirol N-3 (trade name of polystyrene produced by Organsko Kemijska Industrija) was purified by repeated precipitation of with methanol from a benzene solution. After three precipitations the polymer was dried under vacuum to constant weight. Polyacrylonitrile was prepared by slurry polymerization as described by Wilkinson.7 The styrene- and acrylonitrile block copolymer was prepared according to the method of Frankel and et a1.8with n-butyllithium as initiator.

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141

Samples of azeotropic SAN copolymer of different molecular weights were prepared by suspension polymerization at 70 f 1C in the presence of 2,2'-azobis-2-methylpropionitrile of different concentrations. Table I1 shows the characteristics of these samples.
TABLE I1
Molecular Weights of SAN Copolymer of Aseol,ropic Coiiipositiori

0.504 1.020 1.178 1.418


a

142 000 370 000 466 700 623 700


=

Calculated according to the data of Shimura et al.? [ v ]

36 X

MP2.

Intrinsic viscosities were measured in a Cannon-Fenske capillary viscometer, No. 100, in methyl ethyl ketone a t 30 f 0.01"C.

Pyrolysis Apparatus, Gas Chromatograph, and Experimental Conditions


The pyrolysis apparatus used in this study has been described elsewhere. lo The analysis of the decomposition products was carried out with the Model 800 Perkin-Elmer chromatograph, which was connected to the pyrolyzer by a short precut glass column. The analysis was carried out under the following conditions: column, Chromosorb P 30-60 mesh, 7 X 0.6 cm; analytical column, 20% poly(propy1ene glycol) UC oil LB-550-X on Chromosorb P 30-60 mesh, 200 X 0.6 cm, temperature 25-200C; carrier gas, Nz; sample used, 1-5 mg.

RESULTS AND DISCUSSION Determination of the Pyrolyzate Composition


On decomposition of SAN copolymers a t a temperature of 645C (Fig. 1) the following components were identified by calibration against pure substances: acetonitrile, acrylonitrile, propionitrile, benzene, allylcyanide, toluene, ethylbenzene, styrene, a-methylstyrene, diethylbenzene, and ethylvinylbenzene. Quantitative analysis of the decomposition products was performed by measuring the peak area and using a calibration curve obtained for pure components. The quantitative yeilds of the individual components per milligram of sample is shown in Figure 2. Figure 2 shows that, in addition to styrene and acrylonitrile the identified components obtained in the largest amounts are propionitrile, toluene, benzene and a-methylstyrene. The yield of acetonitrile from copolymers containing 31-63 wt-% of acrylonitrile amounts to 2-4 wt-%. When the AN content is below 31 wt-yo, acetonitrile is fourid in coiicentration below

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VUKOVIC AND GNJATOVIC

ETHYL VINYLBENZENE 0IETHYlBENZ"hK

>

L-flETHY1STYRENE STYRENE

> TOLUCNE
x 5000
ALL YLCYANIDE

> >
\

BEN2LN.C PROPIONITRJLE ACRYLONITRILZ

ACCTONlTR/LT

--

GAS fRACTloN

. START 1000

Fig. 1. Typical chromatogramof the products of azeotropic SAN copolymer. Pyrolysis temperature 645C; column, 20% poly(propy1ene glycol) UC oil LB-550-X on Chromosorb P 30-60 mesh, 200 X 0.6 cm; carrier gas Nz, 38 ml/min.

1 wt-%. Figure 2 shows that the yield of component derived from styrene sequences in the copolymer decreases linearly with decreasing styrene concentration in the copolymer and that the yield of components derived from acrylonitrile sequences varies according to a curves having a maximum a t a n acrylonitrile content in the copolymer of about 50 wt-%. It is also evident from Figure 2 that the total amount of identified products is less than 50 wt-%, while other products representing gaseous and heavy components are not identified. The fact that propionitrile is completely separated from acrylonitrile and benzene was utilized for construction of Figure 3, which shows the difference in yields of propionitrile of the random copolymer at different acrylonitrile contents, compared with the yields of propionitrile obtained by decomposition of the mixture of styrene and acrylonitrile homopolymers. Figure 3 shows a pronounced difference in propionitrile yield be-

STYRENEACRYLONITRILE COPOLYMER

143

tween the random copolymer and the mixture of homopolymers a t all the compositions and the important effect of copolymer composition on the propionitrile yield when the copolymer contains 60 mole-yo or more of AN. It is apparent that a t a higher acrylonitrile content the relative propio-

STYRENE ACRYLONITRILE PROPI0Nl~RlL.E

0 0

TOLUENE BLNZENE ~C-MLTHYLSTYRLNE

20

30 M x) 60 10 80 w COPOLYMER COi'lPOSITION IAN Wt. %I

Fig. 2 . Content of various components of the pyrolyzate of random SAN copolymer of different compositions calculated on the sample weight. Pyrolysis temperature 645OC, in Nz stream.
\

PROPfONiTRlLE FOR COPOLYMU?


l u

#O

90 80 70 60 50 10 30 20 {O 0 COPOLYMER C(WPOSIT/ON/AN mole%/

Fig. 3. Propionitrile yields on decomposition of SAN copolymer of different compositions and of the homopolymer mixture versus the acrylonitrile content in the sample. Pyrolysis temperature 645"C, in NL stream.

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VUKOVIC AND GNJATOVIC

t 0 20 30 M 50 6 0 70 do 90 KW COPDL YH@ MtPOJfTlON /M mol.;c /

Fig. 4. Calibration curve for the determination of the copolymer composition. Styrene content of the pyrolyaate during the decomposition of random SAN copolymers of different compositions, calculated on the total sample weight. Pyrolysis temperature 645OC, in Nzstream.

SWw6m&am7MIWm PYRCX YSIS 1IP ERAlURE /TI

Fig. 5. Effect of decomposition temperature on the yields of styrene and acrylonitrile in the decomposition of aaeotropic SAN copolymer in a stream of Nz. Yields were calculated on the total sample weight.

STYRENE ACRYLONfTR/LE

, .
"

1 2 3 4 5 MOLECULAR WEIOHT / f i v x a - 5 /

Fig. 6 . Effect of the molecular weight of azeotropic SAN copolymer on the styrene and acryloriitrile yields. Calculations based on the total sample weight. Pyrolysis temperature 645"C, in Ne stream.

STYRENEACRYLONITRILE COPOLYMER

145

nitrile yield is smaller as a consequenceof the random SAN copolymer structure. For different polystyrene and polyacrylonitrile mixtures, the propionitrile, styrene, and acrylonitrile yields remain constant a t all homopolymer ratios. The block copolymer shows the same relative yield of propionitrile, acrylonitrile, and styrene as the corresponding mixtures and it is impossible to distinguish it from the homopolymer blend. The styrene yield expressed in weight per cent depends linearly on the copolymer composition expressed in mole per cent AN, so that the copolymer'composition can easily be determined (Fig. 4). Styrene and acrylonitrile yields of the decomposition of SAN coploymers of different compositions obtained in this study are different from the yield percentages reported by Shibasaki and Kambe.3 We suppose that this difference may be atrributable to a difference in the apparatus used3r6and of a difference in the separation of the components identified in the pyrolyzate (Fig. 1). Figure 1 shows that the acetonitrile and propionitrile peaks appear before and behind the acrylonitrile peak. Figure 2 shows that the concentration of these may have a significant effect on the differences in results. The same applies to the styrene content of the copolymer, because the a-methylstyrene and ethylbenzene peaks are completely separated from this of styrene.

Effect of Decomposition Temperature


The effect of the decomposition temperature in the range 500-8GOO"C on the yields of styrene and acrylonitrile w a s studied. Figure 5 shows that the acrylonitrile yield continues to increase up to 700C. Above this temperature the decomposition of acrylonitrile units begins, resulting in an increase of the content of more volatile components and decrease of the acrylonitrile content. The same figure shows that the increase of the temperature from 500 to 700C has no influence on the styrene yield. At above 700C the styrene yield also decreases as a consequence of decomposition of the styrene units.

Effect of Molecular Weight


I n order to examine the effect of molecular weight on the styrene and acrylonitrile yields, samples of azeotropic SAN copolymers of different molecular weights were pyrolyzed a t 645C. Figure 6 shows the yields of styrene and acrylonitrile monomers depending on the change of the molecular weight. It is apparent that the styrene yield is decreased by an insignificant amount and the acrylonitrile yield remains constant with increasing molecular weights.
The authors wish to express their thanks to Dr. 11. FleJ and Dr. D. Deur-Siftar for helpful discussionsand interest in this work, and to Mi-. Z. SliepEevi6 for microanalysis.

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References
1. J. Voight, Kunststofe, 51,18 (1961). 2. P. Lebel Rubber Plastics Age, 46,677 (1965). 3. J. Shibasaki and H. Kambe, Kohnshi Kagaku, 21,71 (1964). 4. J. Shibasaki, Kohnshi Kagalcu, 21,125 (1964). 5. J. Shibasaki, J. Polym. Sci., A-I, 5,21 (1967). 6. F. A. Lehman and G. M. Brauer, Anal. C h m . , 33,873 (1961). 7. W. K. Wilkinson in MacrmlecuZar Syntheses, Vol. 11, J. lt. Elliott, Ed., Wiley, New York, 1966, p. 78. 8. M. Frankel, A. Otolenghi, M. Alabeck, and A. Zilkha, J . Chem.SOC, 1959,5858. 9. J. Shimura, J. Mita, and H. Kttmbe, J. Polym. Sci.B, 2,403 (1964). 10. D. Deur-Siftar, T. Bistrirki, and T. Tandi, J . Chromatog., 24,404 (1966).

Received April 4,1969

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